WO2012107689A1 - Polymerisation radicalaire de l'ethylene amorcee par des peroxydes organiques a haute productivite - Google Patents

Polymerisation radicalaire de l'ethylene amorcee par des peroxydes organiques a haute productivite Download PDF

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Publication number
WO2012107689A1
WO2012107689A1 PCT/FR2012/050270 FR2012050270W WO2012107689A1 WO 2012107689 A1 WO2012107689 A1 WO 2012107689A1 FR 2012050270 W FR2012050270 W FR 2012050270W WO 2012107689 A1 WO2012107689 A1 WO 2012107689A1
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WO
WIPO (PCT)
Prior art keywords
polymerization
ethylene
alkyl group
agents
initiator
Prior art date
Application number
PCT/FR2012/050270
Other languages
English (en)
French (fr)
Inventor
Pascal Nicol
Serge Hub
Original Assignee
Arkema France
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=44140892&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2012107689(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to US13/983,787 priority Critical patent/US9045571B2/en
Priority to ES12707885T priority patent/ES2524692T5/es
Priority to EP12707885.5A priority patent/EP2673307B2/fr
Priority to KR1020137023520A priority patent/KR101838771B1/ko
Priority to CA2825190A priority patent/CA2825190C/fr
Application filed by Arkema France filed Critical Arkema France
Priority to JP2013553011A priority patent/JP5859028B2/ja
Priority to CN201280007821.7A priority patent/CN103339155B/zh
Priority to BR112013020243A priority patent/BR112013020243B1/pt
Priority to MYPI2013002951A priority patent/MY181887A/en
Priority to MX2013009207A priority patent/MX2013009207A/es
Publication of WO2012107689A1 publication Critical patent/WO2012107689A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen

Definitions

  • the present invention relates to a process for producing polyethylene or a copolymer of ethylene by high pressure polymerization in the presence of a particular peroxide polymerization initiator in a particular temperature range.
  • US Pat. No. 2,650,913 discloses a process for the polymerization of ethylene in the presence of a 2,2-bis (tertiary butyl peroxy) butane initiator, but this initiator leads to a low productivity (see Example 1 of this document). document 3 below). Also known is FR 2946653 which discloses 2,2-di- (t-amyl peroxy) propane, but it is absolutely not used as an initiator.
  • R1 and R8 are independently (C2-C6) alkyl
  • R2, R3, R6 and R7 are independently (C1-C5) alkyl
  • R4 and R5 are independently (C1-C6) alkyl
  • the polymerization or copolymerization is initiated at an initiation temperature ranging from 150 to 200 ° C., in the presence of a peroxidic polymerization initiator chosen from peroxidic compounds of formula
  • R2, R3, R6 and R7 independently represent a C 1 -C 5 alkyl group
  • R1 and R8 independently represent a C2-C4 alkyl group.
  • the polymerization initiator is generally diluted in a solvent or a mixture of solvents.
  • the solvent (s) may be selected from C 1 -C 20 alkanes.
  • the polymerization or copolymerization is carried out at a pressure ranging from 500 to 3000 bar, preferably from 1200 to 3000 bar, better still from 1200 to 2600 bar.
  • reaction is allowed to proceed until the final temperature returns to the same level as the initial temperature (ie, a test time of about 25 to 50 minutes).
  • the productivity is expressed in grams of polyethylene produced per gram of peroxide initiator used.
  • the use of the initiator 2,2-di (tert-amylperoxy) butane during a polymerization at a temperature between 150 and 200 ° C thus allows to obtain a high conversion and productivity.
  • test 1 and 2 Additional tests were carried out in order to compare the process for producing polyethylene or an ethylene copolymer according to the invention (tests 1 and 2 below) with a process according to the prior art (according to the US document 2,650,913 in which the initiator is 2,2-bis- (tertiary butyl peroxy). Only in the case of the initiators of tests 1 and 2, it is possible to obtain a productivity higher than 3000 g / g with a conversion to a polymer of between 13% and 25%, whereas with the aforementioned initiator referred to in document US Pat. No. 2,650,913, these objectives are not achieved.
  • Quantity of low density polyethylene produced 30.7 g
  • a conventional polymerization of the ethylene according to the invention is carried out with the initiator 2,2-di (tert-butylperoxy) butane.
  • the priming is carried out with 10.2 mg of 2,2-di (tert-butylperoxy) butane.
  • Quantity of low density polyethylene produced 24.6 g

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)
  • Polymerisation Methods In General (AREA)
PCT/FR2012/050270 2011-02-10 2012-02-08 Polymerisation radicalaire de l'ethylene amorcee par des peroxydes organiques a haute productivite WO2012107689A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
MX2013009207A MX2013009207A (es) 2011-02-10 2012-02-08 Polimerizacion por radicales libres de etileno iniciada por peroxidos organicos con alta productividad.
ES12707885T ES2524692T5 (es) 2011-02-10 2012-02-08 Polimerización por radicales de etileno cebada por peróxidos orgánicos con alta productividad
EP12707885.5A EP2673307B2 (fr) 2011-02-10 2012-02-08 Polymerisation radicalaire de l'ethylene amorcee par des peroxydes organiques a haute productivite
KR1020137023520A KR101838771B1 (ko) 2011-02-10 2012-02-08 고생산성을 갖는 유기 과산화물에 의해 개시되는 에틸렌의 자유 라디칼 중합
CA2825190A CA2825190C (fr) 2011-02-10 2012-02-08 Polymerisation radicalaire de l'ethylene amorcee par des peroxydes organiques a haute productivite
US13/983,787 US9045571B2 (en) 2011-02-10 2012-02-08 Free radical polymerisation of ethylene initiated by organic peroxides with high productivity
JP2013553011A JP5859028B2 (ja) 2011-02-10 2012-02-08 有機過酸化物によって開始する生産性の高いエチレンのフリーラジカル重合
CN201280007821.7A CN103339155B (zh) 2011-02-10 2012-02-08 具有高生产率的由有机过氧化物引发的乙烯自由基聚合反应
BR112013020243A BR112013020243B1 (pt) 2011-02-10 2012-02-08 polimerização de radical livre de etileno iniciada por peroxidos organicos com alta produtividade
MYPI2013002951A MY181887A (en) 2011-02-10 2012-02-08 Free radical polymerization of ethylene initiated by organic peroxide with high productivity

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1151086 2011-02-10
FR1151086A FR2971510B1 (fr) 2011-02-10 2011-02-10 Polymerisation radicalaire de l'ethylene amorcee par des peroxydes organiques a haute productivite

Publications (1)

Publication Number Publication Date
WO2012107689A1 true WO2012107689A1 (fr) 2012-08-16

Family

ID=44140892

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FR2012/050270 WO2012107689A1 (fr) 2011-02-10 2012-02-08 Polymerisation radicalaire de l'ethylene amorcee par des peroxydes organiques a haute productivite

Country Status (13)

Country Link
US (1) US9045571B2 (pt)
EP (1) EP2673307B2 (pt)
JP (2) JP5859028B2 (pt)
KR (1) KR101838771B1 (pt)
CN (2) CN103339155B (pt)
BR (1) BR112013020243B1 (pt)
CA (1) CA2825190C (pt)
CO (1) CO6781559A2 (pt)
ES (1) ES2524692T5 (pt)
FR (1) FR2971510B1 (pt)
MX (1) MX2013009207A (pt)
MY (1) MY181887A (pt)
WO (1) WO2012107689A1 (pt)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013107932A (ja) * 2011-11-17 2013-06-06 Three Bond Co Ltd 熱硬化性組成物
FR3041645A1 (fr) * 2015-09-29 2017-03-31 Arkema France Polymerisation radicalaire de l'ethylene amorcee par un couple de peroxydes organiques a haute productivite
FR3047485A1 (fr) * 2016-02-10 2017-08-11 Arkema France Compositions de peroxydes organiques et pre- melange polymere
CN107892728A (zh) * 2017-11-27 2018-04-10 重庆长江造型材料（集团）股份有限公司 纳米填料支撑剂的制备方法
EP3523334B1 (en) 2016-10-04 2020-08-19 Nouryon Chemicals International B.V. Process for manufacturing polyethylene

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2971510B1 (fr) * 2011-02-10 2013-03-22 Arkema France Polymerisation radicalaire de l'ethylene amorcee par des peroxydes organiques a haute productivite
KR101748971B1 (ko) * 2015-12-24 2017-06-20 한화토탈 주식회사 태양전지 봉지재 시트용 에틸렌 비닐아세테이트 공중합체 수지의 제조방법 및 그 제조방법으로 제조된 수지
KR101699183B1 (ko) * 2015-12-24 2017-01-23 한화토탈 주식회사 에틸렌 비닐아세테이트 공중합체 수지의 제조방법 및 이로부터 제조된 수지와 이를 이용하여 제조된 태양전지 봉지재용 시트
KR101757565B1 (ko) * 2015-12-29 2017-07-12 한화토탈 주식회사 폴리에틸렌 또는 폴리에틸렌 비닐아세테이트 공중합체의 제조 방법

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EP0259537A2 (en) 1986-09-09 1988-03-16 ATOCHEM NORTH AMERICA, INC. (a Pennsylvania corp.) Process for reducing residual monomers in low viscosity polymer-polyols
EP0273090A1 (en) 1987-01-02 1988-07-06 ATOCHEM NORTH AMERICA, INC. (a Pennsylvania corp.) Solution polymerization of acrylic acid derived monomers using tertiary alkyl( C5)-hydroperoxides
US20060149004A1 (en) 2004-11-19 2006-07-06 Samsung Total Petrochemicals Co., Ltd. Method of ethylene polymerization for producing products having various properties with high productivity and a tubular reactor used therefor
US20070032614A1 (en) 2005-08-05 2007-02-08 Goossens Ivo T Process and apparatus for manufacturing ethylene polymers and copolymers
WO2008112373A1 (en) * 2007-03-09 2008-09-18 Dow Global Technologies Inc. A free radical initiator system and a high pressure, freeradical polymerization process for producing a low density polyethylene polymer
US20080226891A1 (en) 2007-03-12 2008-09-18 Kansai Paint Co. Ltd. Method for making multilayer coating film
FR2946653A1 (fr) 2009-06-15 2010-12-17 Arkema France Procede de fabrication d'une composition melange-maitre comprenant un peroxyde organique

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Publication number Priority date Publication date Assignee Title
US2650913A (en) 1950-03-23 1953-09-01 Monsanto Chemicals 2, 2-bis-(tertiary butyl peroxy) butane catalyst for ethylene polymerization
EP0259537A2 (en) 1986-09-09 1988-03-16 ATOCHEM NORTH AMERICA, INC. (a Pennsylvania corp.) Process for reducing residual monomers in low viscosity polymer-polyols
EP0273090A1 (en) 1987-01-02 1988-07-06 ATOCHEM NORTH AMERICA, INC. (a Pennsylvania corp.) Solution polymerization of acrylic acid derived monomers using tertiary alkyl( C5)-hydroperoxides
US20060149004A1 (en) 2004-11-19 2006-07-06 Samsung Total Petrochemicals Co., Ltd. Method of ethylene polymerization for producing products having various properties with high productivity and a tubular reactor used therefor
US20070032614A1 (en) 2005-08-05 2007-02-08 Goossens Ivo T Process and apparatus for manufacturing ethylene polymers and copolymers
WO2008112373A1 (en) * 2007-03-09 2008-09-18 Dow Global Technologies Inc. A free radical initiator system and a high pressure, freeradical polymerization process for producing a low density polyethylene polymer
US20080226891A1 (en) 2007-03-12 2008-09-18 Kansai Paint Co. Ltd. Method for making multilayer coating film
FR2946653A1 (fr) 2009-06-15 2010-12-17 Arkema France Procede de fabrication d'une composition melange-maitre comprenant un peroxyde organique

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013107932A (ja) * 2011-11-17 2013-06-06 Three Bond Co Ltd 熱硬化性組成物
FR3041645A1 (fr) * 2015-09-29 2017-03-31 Arkema France Polymerisation radicalaire de l'ethylene amorcee par un couple de peroxydes organiques a haute productivite
WO2017055748A1 (fr) * 2015-09-29 2017-04-06 Arkema France Polymérisation radicalaire de l'éthylène amorcée par un couple de peroxydes organiques à haute productivité
US10189921B2 (en) 2015-09-29 2019-01-29 Arkema France Radical polymerisation of ethylene initiated by a couple of organic peroxides with high productivity
RU2742275C1 (ru) * 2015-09-29 2021-02-04 Аркема Франс Радикальная полимеризация этилена, инициируемая парой высокопроизводительных органических пероксидов
FR3047485A1 (fr) * 2016-02-10 2017-08-11 Arkema France Compositions de peroxydes organiques et pre- melange polymere
WO2017137710A1 (fr) * 2016-02-10 2017-08-17 Arkema France Composition de peroxydes organiques et pré-melange polymère
EP3523334B1 (en) 2016-10-04 2020-08-19 Nouryon Chemicals International B.V. Process for manufacturing polyethylene
CN107892728A (zh) * 2017-11-27 2018-04-10 重庆长江造型材料（集团）股份有限公司 纳米填料支撑剂的制备方法

Also Published As

Publication number Publication date
MY181887A (en) 2021-01-12
ES2524692T5 (es) 2022-11-02
JP6161680B2 (ja) 2017-07-12
FR2971510B1 (fr) 2013-03-22
JP5859028B2 (ja) 2016-02-10
CA2825190A1 (fr) 2012-08-16
KR20140048095A (ko) 2014-04-23
CA2825190C (fr) 2018-11-20
CN103339155B (zh) 2016-08-10
EP2673307B2 (fr) 2022-06-22
CN106046213A (zh) 2016-10-26
BR112013020243B1 (pt) 2020-04-22
CN106046213B (zh) 2018-09-18
BR112013020243A2 (pt) 2016-10-18
MX2013009207A (es) 2013-08-29
US20130310518A1 (en) 2013-11-21
US9045571B2 (en) 2015-06-02
EP2673307A1 (fr) 2013-12-18
ES2524692T3 (es) 2014-12-11
EP2673307B1 (fr) 2014-09-17
JP2014505152A (ja) 2014-02-27
FR2971510A1 (fr) 2012-08-17
CN103339155A (zh) 2013-10-02
JP2016094617A (ja) 2016-05-26
CO6781559A2 (es) 2013-10-31
KR101838771B1 (ko) 2018-03-14

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